EP1029907B1 - Process for mechanical chemical polishing of a layer of aluminium or aluminium alloy conducting material - Google Patents
Process for mechanical chemical polishing of a layer of aluminium or aluminium alloy conducting material Download PDFInfo
- Publication number
- EP1029907B1 EP1029907B1 EP00810129A EP00810129A EP1029907B1 EP 1029907 B1 EP1029907 B1 EP 1029907B1 EP 00810129 A EP00810129 A EP 00810129A EP 00810129 A EP00810129 A EP 00810129A EP 1029907 B1 EP1029907 B1 EP 1029907B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- aluminium
- process according
- colloidal silica
- abrasive
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000004411 aluminium Substances 0.000 title claims abstract description 44
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 44
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000005498 polishing Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 27
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 18
- 239000000126 substance Substances 0.000 title claims abstract description 15
- 239000004020 conductor Substances 0.000 title claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000000203 mixture Substances 0.000 claims abstract description 34
- 239000008119 colloidal silica Substances 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 24
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 18
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 claims abstract description 9
- 239000004065 semiconductor Substances 0.000 claims abstract description 7
- 238000004377 microelectronic Methods 0.000 claims abstract description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 32
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical class OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 2
- ICIWUVCWSCSTAQ-UHFFFAOYSA-N iodic acid Chemical class OI(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 18
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 238000005530 etching Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000003082 abrasive agent Substances 0.000 description 3
- 229910021485 fumed silica Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000007517 polishing process Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 description 1
- -1 aluminium-silicon-copper Chemical compound 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical class C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
Definitions
- the present invention relates to a process for mechanical chemical polishing of a layer of an aluminium or aluminium alloy conducting material used in the microelectronics industry for semi-conductors as material which constitutes interconnecting tracks.
- interconnecting tracks Electronic devices made on a silicon slice must be connected to each other by means of interconnecting tracks to constitute the desired electronic circuit.
- these interconnecting tracks are most often defined using an aluminium-based film.
- the aluminium can be associated with silicon or (and) copper in weak proportions in order to increase its resistance to electromigration.
- the interconnecting tracks of semi-conductors are usually made according to the following sequence: an aluminium or aluminium alloy film approximately 1 ⁇ m thick is deposited by bombardment of an aluminium or aluminium alloy target by means of a beam of electrons or beam of ions (sputtering); the design of the interconnecting circuit is then transferred there by photolithography then by reactive ionic etching (RIE).
- RIE reactive ionic etching
- the tracks thus defined must be electrically isolated, they are also covered with a dielectric layer, usually based on silicon oxide, most often obtained by decomposition in the vapor phase of tetraethylorthosilicate (TEOS). This layer is then planarized by mechanical chemical polishing.
- the damascene process constitutes an alternative solution which allows interconnecting tracks to be made of aluminium whilst reducing the number of stages required. It consists of depositing a silicon oxide based dielectric layer on a substrate. In this dielectric layer, the contact holes and trenches which reproduce the design of the interconnecting circuit are then formed by two photolithographies and successive reactive ionic etchings. An aluminium or aluminium alloy layer is then deposited, which is polished by mechanical chemical polishing until the surface of the dielectric layer is reached. The aluminium thus remains only in the contacts and the trenches.
- the damascene process allow problems linked to the reactive ionic etching of aluminium to be avoided: poor selectivity of aluminium etching compared with its counter-mask in resin and difficult control of the profile of aluminium tracks.
- aluminium polishing stage should thus not only be uniform but also result in an excellent surface state.
- aluminium is a soft and malleable metal which is difficult to polish without scratches.
- EP-A-0 779 655 It was proposed in EP-A-0 779 655 to use an abrasive composition comprising a suspension of fumed silica for polishing aluminium or aluminium alloy surfaces.
- WO-A-97/13889 describes a process intended for polishing aluminium, copper, nickel or tantalum films using an abrasive solution comprising a suspension of aluminium oxide particles.
- EP-A-0 520 109 describes a primary polishing process for silicon trenches using a composition comprised of a colloidal solution of silica stabilized by ammonium hydroxide, a bactericide of the quaternary ammonium hydroxide family, and up to 0.1% by weight of chlorite or sodium hypochlorite.
- EP-A-0 853 335 describes a selective polishing process between a silicon oxide layer and a silicon nitride layer using a modified slurry obtained by combining a slurry with a tetramethylammonium salt, a base and hydrogen peroxide, in which the ratio by volume of slurry to hydrogen peroxide is high, particularly comprised between 200 and 500 to 1.
- EP-A-0 896 042 describes a mechanical chemical polishing composition
- a compound capable of attacking tungsten such as hydrogen peroxide and at least one tungsten attack inhibitor such as tetraalkylammonium hydroxide, and the pH of which is less than 7.
- a subject of the present invention is therefore a process for mechanical chemical polishing of a layer of an aluminium or aluminium alloy conducting material used in the microelectronics semi-conductors industry, characterized in that a layer of said material is abraded using an abrasive composition comprising an alkaline aqueous suspension of individualized colloidal silica particles not linked to each other by siloxane bonds, a tetralkylammonium hydroxide and an oxidizing agent.
- the oxidizing agent is responsible for improving the polishing properties of abrasive compositions of the invention, whilst the tetraalkylammonium hydroxide stabilizes the composition.
- the abrasive compositions used according to the invention will notably have a pH comprised between 8 and 12, preferably between 10.5 and 11.
- abrasive compositions can be obtained, for example, using a silica colloidal solution stabilized with sodium.
- This colloidal solution of silica will thus be treated on a cation exchange resin to eliminate the sodium present, then by tetramethylammonium hydroxide to obtain a stable alkaline aqueous suspension, a subject of the present invention.
- Abrasive compositions advantageous for use according to the invention are obtained using colloidal silica with individualized particles, not linked to each other by siloxane bonds and having average particle diameters comprised between 12 nm and 100 nm, preferably between 35 nm and 50 nm and very particularly of approximately 50 nm.
- the abrasive particles are advantageously present in a concentration by weight comprised between 5% and 50%, preferably between 25% and 35%, and very particularly in a concentration of approximately 30%.
- the tetraalkylammonium hydroxide used to stabilize the abrasive compositions according to the invention is preferably chosen from tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and most particularly tetramethylammonium hydroxide.
- This tetraalkylammonium hydroxide could preferably be used at a concentration comprised between 0.1% by weight and 1% by weight relative to the initial silica and most particularly at a concentration of approximately 0.4% by weight relative to the initial silica.
- the abrasive compositions used in the invention preferably contain between 0.5% and 10% by volume of oxidizing agent.
- oxidizing agent is notably chosen from chlorates, perchlorates, chlorites, iodates, nitrates, sulphates, persulphates, peroxides, ozonized water and hydrogen peroxide.
- the oxidizing agent will preferably be hydrogen peroxide.
- a preferred composition above is characterized in that the quantity of hydrogen peroxide diluted to 30% present in said abrasive composition is comprised between 0.5% and 10% by volume relative to the total of said abrasive composition and notably is approximately 7.5% by volume relative to the total of said abrasive composition.
- compositions used in the invention have remarkable properties which justify their use in the polishing of a layer in an aluminium or aluminium alloy based conducting material, being able to be for example an aluminium-copper alloy or an aluminium-silicon-copper alloy.
- a subject of the present Application is the use of an abrasive composition
- an abrasive composition comprising an alkaline aqueous suspension of individualized colloidal silica particles not linked to each other by siloxane bonds, a tetraalkylammonium hydroxide and an oxidizing agent for mechanical chemical polishing an aluminium or aluminium alloy conducting material used in the microelectronics semi-conductors industry.
- Example of mechanical chemical polishing with an abrasive identical to that of example 1, without the addition of hydrogen peroxide Using slices identical to those in example 2 and under the same operating conditions as those in example 2 and using an alkaline aqueous suspension of colloidal silica stabilized by 0.4% by weight of tetramethylammonium hydroxide, the characteristics of which are the following:
- this suspension generates numerous scratches on the surface of the aluminium. This poor surface state forbids the use of this process for making interconnecting tracks in aluminium using the damascene process.
- Example of mechanical chemical polishing with an abrasive comprising an alkaline aqueous suspension of colloidal silica stabilized by 1.2% by weight of NH 3 (Klebosol® 30 N 50 PHN from Clariant France SA) and comprising 7.5% by volume of hydrogen peroxide diluted to 30%.
- NH 3 Kelbosol® 30 N 50 PHN from Clariant France SA
- Example of mechanical chemical polishing with an abrasive comprising an acidic aqueous suspension of colloidal silica (Klebosol® 30 H 50 from Clariant France SA) and 7.5% by volume of hydrogen peroxide diluted to 30%.
- an acidic aqueous suspension of colloidal silica the characteristics of which are the following:
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Conductive Materials (AREA)
- ing And Chemical Polishing (AREA)
- Polishing Bodies And Polishing Tools (AREA)
- Chemically Coating (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Non-Insulated Conductors (AREA)
Abstract
Description
- The present invention relates to a process for mechanical chemical polishing of a layer of an aluminium or aluminium alloy conducting material used in the microelectronics industry for semi-conductors as material which constitutes interconnecting tracks.
- Electronic devices made on a silicon slice must be connected to each other by means of interconnecting tracks to constitute the desired electronic circuit. Currently, these interconnecting tracks are most often defined using an aluminium-based film. The aluminium can be associated with silicon or (and) copper in weak proportions in order to increase its resistance to electromigration.
- The interconnecting tracks of semi-conductors are usually made according to the following sequence: an aluminium or aluminium alloy film approximately 1 µm thick is deposited by bombardment of an aluminium or aluminium alloy target by means of a beam of electrons or beam of ions (sputtering); the design of the interconnecting circuit is then transferred there by photolithography then by reactive ionic etching (RIE). The tracks thus defined must be electrically isolated, they are also covered with a dielectric layer, usually based on silicon oxide, most often obtained by decomposition in the vapor phase of tetraethylorthosilicate (TEOS). This layer is then planarized by mechanical chemical polishing.
- The damascene process constitutes an alternative solution which allows interconnecting tracks to be made of aluminium whilst reducing the number of stages required. It consists of depositing a silicon oxide based dielectric layer on a substrate. In this dielectric layer, the contact holes and trenches which reproduce the design of the interconnecting circuit are then formed by two photolithographies and successive reactive ionic etchings. An aluminium or aluminium alloy layer is then deposited, which is polished by mechanical chemical polishing until the surface of the dielectric layer is reached. The aluminium thus remains only in the contacts and the trenches.
- The damascene process allow problems linked to the reactive ionic etching of aluminium to be avoided: poor selectivity of aluminium etching compared with its counter-mask in resin and difficult control of the profile of aluminium tracks.
- To carry out mechanical chemical polishing of the aluminium or aluminium alloy layer, two phenomena must be avoided:
- an attack on the subjacent silicon oxide layer, also called erosion. This introduces ridges locally and is counter-productive to the desired aim of planarization.
- an over-polishing of the interconnecting lines in the trenches, also called "dishing". Not only does this phenomenon also generate ridges, but also reduces the thickness of the interconnecting lines, and for this reason, increases their resistance.
- These two phenomena are mainly due to a poor polishing uniformity of the aluminium or aluminium alloy. In fact, an imperfect removal of the metallic layer generally imposes significant over-polishing to avoid any risk of electric conduction between the different electronic devices, which leads to over-polishing the interconnecting lines and the dielectric zones already revealed.
- The aluminium polishing stage should thus not only be uniform but also result in an excellent surface state. In fact, aluminium is a soft and malleable metal which is difficult to polish without scratches.
- These scratches can be generated in two main ways:
- aluminium oxide, which forms naturally on the surface of aluminium, is a harder material than aluminium. The particles of this aluminium oxide layer, once abraded, can agglomerate then scratch the surface of the aluminium. An abrasive composition must thus be used which minimizes the formation of surface aluminium oxide and/or avoids the agglomeration of abraded aluminium oxide particles,
- the particles which constitute the abrasive composition can also scratch the surface of the aluminium if their form and their roughness are badly controlled, which favors the colloidal suspensions of silica more than abrasives based on fumed silica or aluminium oxide.
- It was proposed in EP-A-0 779 655 to use an abrasive composition comprising a suspension of fumed silica for polishing aluminium or aluminium alloy surfaces.
- WO-A-97/13889 describes a process intended for polishing aluminium, copper, nickel or tantalum films using an abrasive solution comprising a suspension of aluminium oxide particles.
- At a different stage of manufacturing electronic circuits, very much upstream, EP-A-0 520 109 describes a primary polishing process for silicon trenches using a composition comprised of a colloidal solution of silica stabilized by ammonium hydroxide, a bactericide of the quaternary ammonium hydroxide family, and up to 0.1% by weight of chlorite or sodium hypochlorite.
- At yet another different stage of manufacturing electronic circuits, EP-A-0 853 335 describes a selective polishing process between a silicon oxide layer and a silicon nitride layer using a modified slurry obtained by combining a slurry with a tetramethylammonium salt, a base and hydrogen peroxide, in which the ratio by volume of slurry to hydrogen peroxide is high, particularly comprised between 200 and 500 to 1.
- EP-A-0 896 042 describes a mechanical chemical polishing composition comprising a compound capable of attacking tungsten such as hydrogen peroxide and at least one tungsten attack inhibitor such as tetraalkylammonium hydroxide, and the pH of which is less than 7.
- The abrasives currently known and intended for polishing aluminium or aluminium alloy, being essentially aluminium or fumed silica based abrasives, do not allow a satisfactory surface quality to be obtained.
- Now, the Applicant has noted in surprising and unexpected fashion that the use of an alkaline aqueous suspension of colloidal silica stabilized by a tetraalkylammonium hydroxide and associated with a oxidizing agent allowed:
- an increased polishing speed for an aluminium or aluminium alloy plate,
- an excellent aluminium surface state.
- A subject of the present invention is therefore a process for mechanical chemical polishing of a layer of an aluminium or aluminium alloy conducting material used in the microelectronics semi-conductors industry, characterized in that a layer of said material is abraded using an abrasive composition comprising an alkaline aqueous suspension of individualized colloidal silica particles not linked to each other by siloxane bonds, a tetralkylammonium hydroxide and an oxidizing agent.
- According to research carried out by the Applicant, the oxidizing agent is responsible for improving the polishing properties of abrasive compositions of the invention, whilst the tetraalkylammonium hydroxide stabilizes the composition.
- The abrasive compositions used according to the invention will notably have a pH comprised between 8 and 12, preferably between 10.5 and 11.
- These abrasive compositions can be obtained, for example, using a silica colloidal solution stabilized with sodium. This colloidal solution of silica will thus be treated on a cation exchange resin to eliminate the sodium present, then by tetramethylammonium hydroxide to obtain a stable alkaline aqueous suspension, a subject of the present invention.
- Abrasive compositions advantageous for use according to the invention are obtained using colloidal silica with individualized particles, not linked to each other by siloxane bonds and having average particle diameters comprised between 12 nm and 100 nm, preferably between 35 nm and 50 nm and very particularly of approximately 50 nm.
- In all the compositions used according to the invention, the abrasive particles are advantageously present in a concentration by weight comprised between 5% and 50%, preferably between 25% and 35%, and very particularly in a concentration of approximately 30%.
- The tetraalkylammonium hydroxide used to stabilize the abrasive compositions according to the invention is preferably chosen from tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and most particularly tetramethylammonium hydroxide.
- This tetraalkylammonium hydroxide could preferably be used at a concentration comprised between 0.1% by weight and 1% by weight relative to the initial silica and most particularly at a concentration of approximately 0.4% by weight relative to the initial silica.
- The abrasive compositions used in the invention preferably contain between 0.5% and 10% by volume of oxidizing agent. This is notably chosen from chlorates, perchlorates, chlorites, iodates, nitrates, sulphates, persulphates, peroxides, ozonized water and hydrogen peroxide.
- The oxidizing agent will preferably be hydrogen peroxide. A preferred composition above is characterized in that the quantity of hydrogen peroxide diluted to 30% present in said abrasive composition is comprised between 0.5% and 10% by volume relative to the total of said abrasive composition and notably is approximately 7.5% by volume relative to the total of said abrasive composition.
- The compositions used in the invention have remarkable properties which justify their use in the polishing of a layer in an aluminium or aluminium alloy based conducting material, being able to be for example an aluminium-copper alloy or an aluminium-silicon-copper alloy.
- Finally, a subject of the present Application is the use of an abrasive composition comprising an alkaline aqueous suspension of individualized colloidal silica particles not linked to each other by siloxane bonds, a tetraalkylammonium hydroxide and an oxidizing agent for mechanical chemical polishing an aluminium or aluminium alloy conducting material used in the microelectronics semi-conductors industry.
- Preferred conditions of using the polishing processes described above also apply to the other subjects of the invention envisaged above.
- The scope of the invention can be understood better by referring to the examples given below, the aim of which is to explain the advantages of the invention.
- 7.5% by volume of hydrogen peroxide diluted to 30% is added to a suspension of colloidal silica stabilized by 0.4% by weight of tetramethylammonium hydroxide (sample PL 1509 from Clariant France SA), the characteristics of which are as follows:
- pH of the aqueous suspension: 11
- specific surface: 55 m2/g
- average diameter of the elementary particles of colloidal silica: 50 nm
- concentration by weight in colloidal silica: 30%
- An abrasive composition according to the invention is thus obtained.
- On each plate studied, aluminium of 10000 Å thickness is deposited on a layer of 1600 Å silicon oxide. The slices are then polished on a PRESI E 460 polisher with the following polishing conditions:
- applied pressure 0.2 daN/cm2
- turntable speed 30 rpm
- head speed 30 rpm
- abrasive temperature 20°C
- abrasion rate 100 cm3/mn
- fabric IC 1000 furrows from Rodel Products
- an aluminium polishing speed of 1700 Å/mn,
- an excellent surface state (no scratches observed under the optical microscope),
- a polishing non-uniformity equal to 8%.
- Example of mechanical chemical polishing with an abrasive identical to that of example 1, without the addition of hydrogen peroxide. Using slices identical to those in example 2 and under the same operating conditions as those in example 2 and using an alkaline aqueous suspension of colloidal silica stabilized by 0.4% by weight of tetramethylammonium hydroxide, the characteristics of which are the following:
- pH of the aqueous suspension: 11
- specific surface: 55 m2/g
- average diameter of elemental particles of colloidal silica: 50 nm
- concentration by weight in colloidal silica: 30 %
- an aluminium polishing speed of 1450 Å/mn,
- a polishing non-uniformity equal to 15%.
- Moreover, this suspension generates numerous scratches on the surface of the aluminium. This poor surface state forbids the use of this process for making interconnecting tracks in aluminium using the damascene process.
- Example of mechanical chemical polishing with an abrasive comprising an alkaline aqueous suspension of colloidal silica stabilized by 1.2% by weight of NH3 (Klebosol® 30 N 50 PHN from Clariant France SA) and comprising 7.5% by volume of hydrogen peroxide diluted to 30%. Using slices identical to those in example 2 and under the same operating conditions as those in example 2, and using an alkaline aqueous suspension of colloidal silica stabilized by 1.2% by weight of NH3, the characteristics of which are as follows:
- pH of the aqueous suspension: 11
- specific surface: 57 m2/g
- average diameter of the elemental particles of colloidal silica: 50 nm
- concentration by weight in colloidal silica: 30%
- an aluminium polishing speed of 1600 Å/mn,
- a polishing non-uniformity equal to 10%.
- However, it generates numerous scratches on the surface of the aluminium. This poor surface state forbids the use of this process for making interconnecting tracks in aluminium by the damascene process.
- Example of mechanical chemical polishing with an abrasive comprising an acidic aqueous suspension of colloidal silica (Klebosol® 30 H 50 from Clariant France SA) and 7.5% by volume of hydrogen peroxide diluted to 30%. Using slices identical to those in example 2 and under the same operating conditions as those of example 2, using an acidic aqueous suspension of colloidal silica, the characteristics of which are the following:
- pH of the aqueous suspension: 2.2
- specific surface: 54 m2/g
- average diameter of the elemental particles of colloidal silica: 50 nm
- concentration by weight in colloidal silica: 30%
Claims (15)
- A process for mechanical chemical polishing of a layer of an aluminium or aluminium alloy conducting material used in the microelectronics semi-conductors industry, characterized in that said aluminium or aluminium alloy layer is abraded using an abrasive composition which comprises an alkaline aqueous suspension of individualized colloidal silica particles not linked to each other by siloxane bonds, a tetraalkylammonium hydroxide and an oxidizing agent.
- A process according to claim 1, characterized in that the pH of said alkaline aqueous suspension of individualized colloidal silica particles not linked to each other by siloxane bonds is comprised between 8 and 12.
- A process according to one of claims 1 and 2, characterized in that the pH of said alkaline aqueous suspension of individualized colloidal silica particles not linked to each other by siloxane bonds is from 10.5 to 11.
- A process according to one of claims 1 to 3, characterized in that the average diameter of the abrasive particles of individualized colloidal silica particles of said composition is comprised between 12 nm and 100 nm.
- A process according to one of claims 1 to 4, characterized in that the average diameter of the colloidal silica abrasive particles of said composition is comprised between 35 nm and 50 nm.
- A process according to one of claims 1 to 5, characterized in that the concentration by weight in abrasive particles of said composition is comprised between 5% and 50%.
- A process according to one of claims 1 to 6, characterized in that the concentration by weight in abrasive particles of said composition is comprised between 25 and 35%.
- A process according to one of claims 1 to 7, characterized in that the stabilizing agent for individualized colloidal silica particles not linked to each other by siloxane bonds is tetramethylammonium hydroxide, tetraethylammonium hydroxide or tetrapropylammonium hydroxide.
- A process according to one of claims 1 to 8, characterized in that the quantity of tetralkylammonium hydroxide is comprised between 0.1% by weight and 1% by weight relative to the initial silica.
- A process according to one of claims 1 to 9, characterized in that the quantity of tetralkylammonium hydroxide is approximately 0.4% by weight relative to the initial silica.
- A process according to one of claims 1 to 10, characterized in that the oxidizing agent is chosen from chlorates, perchlorates, chlorites, iodates, nitrates, sulphates, persulphates, peroxides, ozonized water and hydrogen peroxide.
- A process according to one of claims 1 to 11, characterized in that the oxidizing agent is hydrogen peroxide.
- A process according to claim 12, characterized in that the quantity of hydrogen peroxide diluted to 30% in said abrasive composition is comprised between 0.5% and 10% by volume relative to the total of said abrasive composition.
- A process according to one of claims 12 and 13, characterized in that the quantity of hydrogen peroxide diluted to 30% in said abrasive composition is approximately 7.5% by volume relative to the total of said abrasive composition.
- Use of an abrasive composition comprising an alkaline aqueous suspension of individualized colloidal silica particles not linked to each other by siloxane bonds, a tetraalkylammonium hydroxide and an oxidizing agent, for mechanical chemical polishing of an aluminium or aluminium alloy conducting material used in the microelectronics semi-conductors industry.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9902005A FR2789998B1 (en) | 1999-02-18 | 1999-02-18 | NOVEL MECHANICAL CHEMICAL POLISHING COMPOSITION OF A LAYER OF ALUMINUM OR ALUMINUM ALLOY CONDUCTIVE MATERIAL |
FR9902005 | 1999-02-18 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1029907A1 EP1029907A1 (en) | 2000-08-23 |
EP1029907B1 true EP1029907B1 (en) | 2003-07-02 |
Family
ID=9542207
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00810129A Expired - Lifetime EP1029907B1 (en) | 1999-02-18 | 2000-02-16 | Process for mechanical chemical polishing of a layer of aluminium or aluminium alloy conducting material |
Country Status (14)
Country | Link |
---|---|
US (1) | US6386950B1 (en) |
EP (1) | EP1029907B1 (en) |
JP (1) | JP2000243734A (en) |
KR (1) | KR100685753B1 (en) |
CN (1) | CN1167109C (en) |
AT (1) | ATE244285T1 (en) |
DE (1) | DE60003591T2 (en) |
DK (1) | DK1029907T3 (en) |
ES (1) | ES2200804T3 (en) |
FR (1) | FR2789998B1 (en) |
ID (1) | ID24802A (en) |
MY (1) | MY128000A (en) |
SG (1) | SG97841A1 (en) |
TW (1) | TWI283703B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SG108285A1 (en) * | 2000-12-04 | 2005-01-28 | Bayer Ag | Polishing slurry for the chemical-mechanical polishing of metal and dielectric structures |
Families Citing this family (18)
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KR100367830B1 (en) * | 2000-12-18 | 2003-01-10 | 제일모직주식회사 | Composition for chemical mechanical polishing |
DE10152993A1 (en) * | 2001-10-26 | 2003-05-08 | Bayer Ag | Composition for the chemical mechanical polishing of metal and metal / dielectric structures with high selectivity |
KR20040094758A (en) * | 2002-03-04 | 2004-11-10 | 가부시키가이샤 후지미인코퍼레이티드 | Polishing composition and method for forming wiring structure |
JP4974447B2 (en) * | 2003-11-26 | 2012-07-11 | 株式会社フジミインコーポレーテッド | Polishing composition and polishing method |
CN100427266C (en) * | 2004-05-31 | 2008-10-22 | 中芯国际集成电路制造(上海)有限公司 | Method and structure for aluminium chemical mechanical polishing and protective layer |
US20080020680A1 (en) * | 2006-07-24 | 2008-01-24 | Cabot Microelectronics Corporation | Rate-enhanced CMP compositions for dielectric films |
DE102006039679B4 (en) * | 2006-08-24 | 2011-02-10 | Audi Ag | Method for machining cylinder running surfaces of a cylinder crankcase or cylinder liners |
CN101143996A (en) * | 2006-09-15 | 2008-03-19 | 安集微电子(上海)有限公司 | Chemical mechanical polishing fluid for polishing polycrystalline silicon |
TWI408216B (en) * | 2007-03-07 | 2013-09-11 | Anji Microelectronics Co Ltd | Application of Polishing Solution in Adjusting Polysilicon / Silica Selectivity Ratio |
EP2268777A4 (en) * | 2008-04-24 | 2011-11-23 | Ppt Res Inc | Stable aqueous slurry suspensions |
EP2356192B1 (en) * | 2008-09-19 | 2020-01-15 | Cabot Microelectronics Corporation | Barrier slurry for low-k dielectrics |
CN102020975B (en) * | 2010-07-21 | 2013-04-03 | 天津晶岭微电子材料有限公司 | Preparation method of magnesium aluminum alloy surface chemically mechanical polishing solution |
CN104736296B (en) * | 2012-08-24 | 2018-08-28 | 艺康美国股份有限公司 | The method for polishing sapphire surface |
EP2969391B1 (en) | 2013-03-15 | 2018-04-25 | Ecolab USA Inc. | Methods of polishing sapphire surfaces |
CN104109481B (en) * | 2014-06-26 | 2016-05-11 | 河北宇天昊远纳米材料有限公司 | A kind of preparation method of sapphire substrate polishing solution |
CN104109482B (en) * | 2014-06-27 | 2016-04-20 | 河北宇天昊远纳米材料有限公司 | A kind of aluminium alloy polishing fluid and preparation method thereof |
US10586914B2 (en) | 2016-10-14 | 2020-03-10 | Applied Materials, Inc. | Method of forming ultra-smooth bottom electrode surface for depositing magnetic tunnel junctions |
CN106752969A (en) * | 2016-11-22 | 2017-05-31 | 启东市清清蔬果农地股份专业合作社 | A kind of polishing fluid of aluminum alloy casing |
Family Cites Families (12)
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DE69108546T2 (en) * | 1991-05-28 | 1995-11-30 | Rodel Inc | Polishing paste made from silica with a low content of sodium and metals. |
US5431777A (en) * | 1992-09-17 | 1995-07-11 | International Business Machines Corporation | Methods and compositions for the selective etching of silicon |
JPH07193034A (en) * | 1993-03-26 | 1995-07-28 | Toshiba Corp | Polishing method |
JP2606156B2 (en) * | 1994-10-14 | 1997-04-30 | 栗田工業株式会社 | Method for collecting abrasive particles |
EP0779655A3 (en) * | 1995-12-14 | 1997-07-16 | International Business Machines Corporation | A method of chemically-mechanically polishing an electronic component |
MY133700A (en) * | 1996-05-15 | 2007-11-30 | Kobe Steel Ltd | Polishing fluid composition and polishing method |
US5866031A (en) * | 1996-06-19 | 1999-02-02 | Sematech, Inc. | Slurry formulation for chemical mechanical polishing of metals |
US5855811A (en) * | 1996-10-03 | 1999-01-05 | Micron Technology, Inc. | Cleaning composition containing tetraalkylammonium salt and use thereof in semiconductor fabrication |
FR2754937B1 (en) * | 1996-10-23 | 1999-01-15 | Hoechst France | NOVEL MECHANICAL AND CHEMICAL POLISHING OF INSULATING MATERIAL LAYERS BASED ON SILICON OR SILICON DERIVATIVES |
EP0853335A3 (en) * | 1997-01-10 | 1999-01-07 | Texas Instruments Incorporated | Slurry and process for the mechano-chemical polishing of semiconductor devices |
ATE214418T1 (en) * | 1997-04-17 | 2002-03-15 | Merck Patent Gmbh | BUFFER SOLUTIONS FOR SUSPENSIONS USABLE FOR CHEMICAL-MECHANICAL POLISHING |
US6083419A (en) * | 1997-07-28 | 2000-07-04 | Cabot Corporation | Polishing composition including an inhibitor of tungsten etching |
-
1999
- 1999-02-18 FR FR9902005A patent/FR2789998B1/en not_active Expired - Fee Related
-
2000
- 2000-02-02 SG SG200000579A patent/SG97841A1/en unknown
- 2000-02-15 JP JP2000036011A patent/JP2000243734A/en active Pending
- 2000-02-16 TW TW089102587A patent/TWI283703B/en not_active IP Right Cessation
- 2000-02-16 MY MYPI20000545A patent/MY128000A/en unknown
- 2000-02-16 DK DK00810129T patent/DK1029907T3/en active
- 2000-02-16 ES ES00810129T patent/ES2200804T3/en not_active Expired - Lifetime
- 2000-02-16 AT AT00810129T patent/ATE244285T1/en active
- 2000-02-16 EP EP00810129A patent/EP1029907B1/en not_active Expired - Lifetime
- 2000-02-16 DE DE60003591T patent/DE60003591T2/en not_active Expired - Lifetime
- 2000-02-17 KR KR1020000007452A patent/KR100685753B1/en not_active IP Right Cessation
- 2000-02-17 US US09/506,045 patent/US6386950B1/en not_active Expired - Lifetime
- 2000-02-18 CN CNB001022407A patent/CN1167109C/en not_active Expired - Fee Related
- 2000-02-18 ID IDP20000127A patent/ID24802A/en unknown
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SG108285A1 (en) * | 2000-12-04 | 2005-01-28 | Bayer Ag | Polishing slurry for the chemical-mechanical polishing of metal and dielectric structures |
Also Published As
Publication number | Publication date |
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MY128000A (en) | 2007-01-31 |
ID24802A (en) | 2000-08-24 |
KR100685753B1 (en) | 2007-02-23 |
CN1264636A (en) | 2000-08-30 |
FR2789998A1 (en) | 2000-08-25 |
DE60003591D1 (en) | 2003-08-07 |
FR2789998B1 (en) | 2005-10-07 |
EP1029907A1 (en) | 2000-08-23 |
KR20000058073A (en) | 2000-09-25 |
SG97841A1 (en) | 2003-08-20 |
CN1167109C (en) | 2004-09-15 |
US6386950B1 (en) | 2002-05-14 |
TWI283703B (en) | 2007-07-11 |
ATE244285T1 (en) | 2003-07-15 |
ES2200804T3 (en) | 2004-03-16 |
DE60003591T2 (en) | 2004-06-03 |
JP2000243734A (en) | 2000-09-08 |
DK1029907T3 (en) | 2003-10-13 |
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